THE HYDROCARBONS

Hydrocarbons are organic compounds that primarily consist of C and H atoms.

They include alkanes, alkenes, alkynes, and aromatic hydrocarbons. Generally,
hydrocarbons are insoluble in water because of they are nonpolar. The main structural
difference among hydrocarbon families is the presence of double or triple bonds between
carbon atoms. Alkanes are saturated hydrocarbons having single bonds. Alkenes and
alkynes are unsaturated hydrocarbons with double or triple bonds, respectively.

HYDROCARBONS

Aliphatic* Aromatic
a) saturated ( alkanes) ( benzene)
b) unsaturated ( alkenes & alkynes)

Figure 2. Aliphatic and Aromatic Hydrocarbons

A. Aliphatic hydrocarbon

A.1 ALKANES
1. saturated hydrocarbons
2. characterized by single bonds between C atoms
3. known as paraffins
4. general formula is CnH2n+2

Molecular and Condensed Structural Formulas for the first ten normal alkanes:
No. of C atoms Molecular formula Structural formula
1 CH4 CH4
2 C2H6 CH3CH3
3 C3H8 CH3CH2CH3
4 C4H10 CH3CH2CH2CH3
5 C5H12 CH3CH2CH2CH2CH3
6 C6H14 CH3CH2CH2CH2CH2CH3
7 C7H16 CH3CH2CH2CH2CH2CH2CH3
8 C8H18 CH3CH2CH2CH2CH2CH2CH2CH3
9 C9H20 CH3CH2CH2CH2CH2CH2CH2CH2CH3
10 C10H22 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
NOMENCLATURE:
Two Basic System:
1. Common name
2. IUPAC name

COMMON NAME :
Some prefixes are adapted to designate special structures.
a. normal ( n ) – refers to a continuous chain of C atoms is present; no branching
group.
Example: CH3-CH2-CH3 CH3-CH2-CH2-CH3
n- propane n – butane
b. iso position: if the methyl branch, -CH3, is bonded to a secondary C atom next to a
terminal C atom.
Example: CH3-CH-CH3 CH3-CH-CH2-CH3
| |
CH3 CH3
isobutane isopentane
c. secondary (sec-) position: if the methyl branch, -CH3, is bonded to any secondary
C atom
Example: CH3-CH2-CH- CH2-CH3 CH3-CH2-CH2-CH-CH2CH3
| |
CH3 CH3
sec-hexane sec-heptane
d. neo position: if the methyl branch, -CH3, is bonded to a tertiary C atom next to the
terminal C atom.
CH3 CH3
| |
Example: CH3-CH2-C-CH3 CH3-CH2-CH2-C-CH3
| |
CH3 CH3
neohexane neoheptane
e. tertiary (tert-) position: if the methyl branch, -CH3, is bonded to any tertiary C atom.
CH3 CH3
| |
Example: CH3-CH2-C-CH2-CH3 CH3-CH2-CH2-C-CH2-CH3
| |
CH3 CH3
tert-heptane tert-octane

IUPAC System of Naming Alkanes:

The IUPAC (International Union of Pure and Applied Chemistry) is composed of
chemists representing chemical societies of several countries. One committee of the
IUPAC, the Commission on Nomenclature of Organic Chemistry has set a system for
naming organic compounds. The last syllable in the name of a compound designates the
family to which it belongs. The alkanes all end in –ane.
IUPAC Rules for Naming Akanes:
1. The name ending for all alkanes/cycloalkanes is –ane.
2. Locate the longest continuous chain of carbon atoms. Assign a parent name.
3. Identify the groups that are not part of the parent chain. Name these as branches.
4. Assign numbers to the group by counting from one end of the chain. A chain has two
ends, and the end we start from is the one that gives the lowest possible numbers to the
group/s.
5. If there are two or more identical groups, the following prefixes are used:
Note: Tabular form
No. of identical groups Prefixes no. of identical groups prefixes
2 di - 5 penta-
3 tri - 6 hexa –
4 tetra -
6. If there are two or more different groups, arrange the names of the branches in
alphabetical order.

7. The four halogens are named by prefixes:

F – flouro Cl – chloro Br – bromo I - iodo
8. cycloalkanes: Number the ring beginning with the substituent of lower alphabetical
order. The numbering of the ring continues either clockwise or counterclockwise that
affords the second and succeeding substituents the lowest possible location numbers.

Examples:
Note: Arrange according to the rules (from simple to complicated examples)
CH3
6 5 4| 3 2 1 Answer: a) 4-methyl hexane ( X )
CH3-CH2-CH-CH2-CH2-CH3 b) 3-methyl hexane ( correct answer)
1 2 3 4 5 6
CH3
6 5 4| 3 2 1 Answer: a) 3- ethyl-4-methyl hexane (correct )
CH3-CH2-CH-CH-CH2-CH3 b) 4-ethyl-3-methyl hexane ( correct )
1 2 3 |4 5 6
CH2-CH3

CH3
6 5 4| 3 2 1 Answer: a) 1,2-dichloro-4-methyl hexane (correct)
CH3-CH2-CH-CH2-CH-CH2-Cl b) 5,6-dichloro-3-methyl hexane (X)
1 2 3 4 |5 6
Cl
H3C CH3 Answer: a) 1,2,4- trimethyl cyclohexane (correct)
b) 1,2,5 -trimethyl cyclohexane (incorrect)
c) 1,3,4 - trimethyl cyclohexane (incorrect)

CH3
Cl Br Answer: a) 2-bromo-4-chloro-1-methylcyclopentane
b) 1-bromo-3-chloro-5-methylcyclopentane
CH3 c) 3-bromo-1-chlro-4-methylcyclopentane

Alkyl groups
An alkyl is a radical group which has one hydrogen atom less from its alkane counterpart.

Important branched alkyl groups:

CH3— methyl CH3CH2— ethyl

CH3CH2CH2— propyl CH3CH2CH2CH2— butyl
CH3 CH3
| |
CH3-CH— isopropyl CH3CHCH2— isobutyl
CH3 CH3
| |
CH3CH2CH— sec.butyl CH3-C— tert.butyl
|
CH3
CH3
|
CH3-C-CH2— neopentyl phenyl
|
CH3

II. ALKENES AND ALKYNES

Hydrocarbons with double and triple bonds make up the alkene and alkyne
family, respectively. Like the alkanes and other hydrocarbons, they are insoluble in water
and are flammable.

ALKENES:
- unsaturated aliphatic hydrocarbons
- characterized by a double bond between two carbon atoms
- general formula is CnH2n
- known as olefin ( oil formers )
 ALKYNES:
- unsaturated aliphatic hydrocarbons
- characterized by a triple bond between two carbon atoms
- general formula is CnH2n-2

NOMENCLATURE and FORMULA:

COMMON NAME:
Note: Add additional rules/steps in naming alkenes and alkynes.
Greek letters, such as, alpha ( α , β , γ etc.) are used to indicate the position of
the double and triple bonds
a. alkenes – alkyl group + ene
b. alkynes – alkyl group + yne

Examples:

CH3CH=CH2 propylene CH3CH=CHCH3 β- butylene

CH2=CH2 ethylene CH2=CHCH2CH3 α - butylene

CH3C≡CH propylyne CH3-C≡C-CH3 β- butylyne

CH≡CH ethylyne CH≡C-CH2CH3 α – butylyne

CH3CHCH=CH2 γ-methyl-α-butylene CH3CHCH2CHCH=CHCH3

| | |
CH3 Cl CH3
γ-chloro-γ-methyl-β-heptylene
CH3CHC≡CH γ-methyl-α-butylyne CH3CHCH2CHCH2C≡CH
| | |
CH3 Cl CH3
γ-chloro-γ-methyl-α-heptylyne

IUPAC NAMING OF ALKENES and ALKYNES:

The rules for naming alkenes and alkynes are basically the same as those of alkanes, but
with two differences. The parent chain must include the double and triple bond even if it
makes it shorter than the others. And the parent alkene and alkyne must be numbered
from whichever end gives the first carbon of the double and triple bond the lower of two
possible numbers. Also, the location number should be given as to where the double and
triple is ( except ethene or propene and ethyne or propyne, where the location will always
be 1).
Examples:

CH3CH=CH2 propene CH3CH=CHCH3 2- butene

CH2=CH2 ethene CH2=CHCH2CH3 1 - butene

CH3C≡CH propyne CH3-C≡C-CH3 2- butyne

CH≡CH ethyne CH≡C-CH2CH3 1 – butyne

CH3CHCH=CH2 3-methyl-1-butene CH3CHCH2CHCH=CHCH3

| | |
CH3 Cl CH3
6-chloro-4-methyl-2-heptene
CH3CHC≡CH 3-methyl-1-butyne CH3CHCH2CHCH2C≡CH
| | |
CH3 Cl CH3
6-chloro-4-methyl-1-heptyne

Alkenes with two or more double bonds are given the suffix –diene, -triene, -tetraene
and so on.

Example:

CH2CH=CHCH2CH=CHCH3 2,5-heptadiene

CH2=CH=C-CH2CH=C-CH2CH3 3-chloro-6-methyl-1,2,5-octatriene
| |
Cl CH3

Cycloalkenes:

Example
Encircle the letter corresponding to the correct name of the compound.

CH2CH3 Answer: a) 3-ethyl-1-methylcyclobutene

b) 1-ethyl-3-methylcyclobutene
H3C

H3C Cl Answer: a) 1-chloro-3-methylcyclopentene

b) 2-chloro-5-methylcyclopentene

CH3 Answer: a) 1,4,6-trimethylcyclohexadiene

b) 1,3,4-trimethyl-1, 4- cyclohexadiene
CH3
H3C
III. AROMATIC HYDROCARBON
The aromatic hydrocarbons include benzene and the aryl derivatives of benzene.
Benzene is a six sided ring drawn with alternating single and double bonds or with a
circle in the middle indicating electron delocalization.
The benzene ring
Any compound with the benzene ring is an aromatic compound, so named
because these compounds have pleasant fragrances before their chemical structures were
discovered. But it turns out that the ring has nothing to do with the smell. Although other
aromatic compounds like aspirin is entirely odorless.

Though the structure of the benzene ring appears to be similar to a triene ( alkene with
three double bonds), their properties, however, are entirely different. Benzene does not
undergo addition reactions as alkenes do, and it is unusually stable to oxidizing agent.

NOMENCLATURE OF BENZENE DERIVATIVES:

The rule for naming benzene containing:
A. One substituent
- give the name of the group followed by the parent name, “ benzene”

Cl NO2 CH2CH3 Br

Chlorobenzene nitrobenzene ethyl benzene bromobenzene

Others however, are named by their common names:

CH3 OH NH2 COOH

Toluene phenol aniline benzoic acid

b. Two substituents
Prefixes or numbers are used as ortho (o) or 1,2; meta (m) or 1,3; and para (p) or 1,4.

Example: Br
Br Br Br

Br Br
1,2 (ortho) 1,3 (meta) 1,4 (para)
CN:O-dibromobenzene
IUPAC: 1,2-dibromobenzene
c. Three or more substituents
- ortho, meta or para are not used when there are more than two substituents present. For
these cases, numbers are used instead.
Note: Transfer the examples to their corresponding groups.
Example:

CH-CH3 isopropyl benzene

|
CH3

Cl

CH3 CN: o-chloro toluene

IUPAC: 2-chloro toluene

NO2
CN: m-bromonitro benzene
IUPAC: 3-bromonitrobenzene

Br

CN: p-ethyl phenol

HO CH2CH3 IUPAC: 4-ethyl phenol

Cl

Cl IUPAC: 1,2,4-trichloro benzene

Cl

CH3

F F IUPAC: 2,5-diflouro-3-iodo toluene

PHYSICAL PROPERTIES OF HYDROCARBONS:

A. Aliphatic hydrocarbons:
1. are odorless, colorless and tasteless
2. their boiling and melting points increase with increasing molecular weight
3. having 1 to 4 carbons, including cycloalkanes, are gases at room temperature.
4. with 5 to 17 carbons are liquids at room temperature
5. containing 18 carbons and above are solids at room temperature.
6. are insoluble in water.
7. are less dense than water.
B. Aromatic hydrocarbons
1. colorless liquid with distinct gasoline-like odor.
2. insoluble in water in alcohol and ether
3. toxic when taken internally
4. mildly carcinogenic
5. harmful when in contact with skin
6. Aromatic amines and nitro compounds, such as aniline and nitrobenzene, cause
methemoglobinemia by initiating redox cycle in the RBC.(Williams et al., 2000)